Powdered cosmetics of hydrophilic hydroxy lower alkyl acrylates and methocrylates

ABSTRACT

COSMETIC PREPARATIONS SUCH AS POWDERS AND THE LIKE ARE PREPARED BY ADDING A POWDERED HYDROPHYLIC ACRYLATE OR METHACRYLATE POLYMER TO THE SELECTED POWDERED COSMETIC INGREDIENTS. THE HYDROPHYLIC POLYMER CAN BE CROSSLINKED.

United States Patent 3,574,822 POWDERED COSMETICS OF HYDROPHILIC HYDROXYLOWER ALKYL A'CRYLATES AND METHOCRYLATES Thomas H. Shepherd, Hopewell,and Francis E. Gould,

Princeton, N..l., assignors to National Patent Development Corporation,New York, N.Y.

No Drawing. Continuation-impart of applications Ser. No. 567,856, July26, 1966, Ser. No. 650,259, June 30, 1967, and Ser. No. 654,044, July 5,1967. This application July 10, 1968, Ser. No. 743,626

Int. Cl. A61k 7/00, 7/02, 7/10 US. Cl. 424-47 12 Claims ABSTRACT OF THEDISCLOSURE Cosmetic preparations such as powders, and the like areprepared by adding a powdered hydrophylic acrylate or methacrylatepolymer to the selected powdered cosmetic ingredients. The hydrophylicpolymer can be crosslinked.

The present application relates to novel cosmetic preparations.

The present application is a continuation-in-part of application Ser.No. 567,856, filed July 26, 1966, now U.S. Pat. 3,520,949, andapplication Ser. No. 654,044, filed July 5, 1967, and application Ser.No. 650,259, filed June 30, 1967, now abandoned.

Cosmetic manufacturers have sought in the past to produce compositionsfor use on human hair and skin which may be easily applied, exihibt nodetrimental effect on the skin and retain their stability for aresonable period of time. Some progress has been made in producingproducts of this type. However, there remains inherent defects in priorpreparations such as creams, lotions, shampoos, dressing, sticks, andthe like which impairs their cosmetic effectiveness. One example of thisis the wellknown tendency of conventional mascara to run when wet bytears or water.

As is well known the various creams used on the body have a tendency tosoil clothing, bed clothes and the like. Lipsticks and suntan creamshave a tendency to be greasy and essences (e.g. perfume) and othervolatile components present in lipstick, creams and lotions have atendency to be lost on standing.

It has hitherto been proposed to employ lacquers for imparting atemporary set to the hair. However, since lacquers include awater-insoluble film-forming ingredient, it has been extremely difficultto remove them from the hair. When it is desired to change the hairstyle, it sometimes becomes necessary to employ a special solvent or apowerful detergent composition, neither of which is readily available inthe home. Lacquers have generally been considered unsatisfactory forapplication to the hair for this reason. A number of water-solublefilm-forming resinous materials have also been proposed for applicationto the hair in order to set it. However, such watersoluble materialshave not been completely satisfactory because of the tendency for theresultant film to become tacky and for the hair to lose its set whenexposed to conditions of high humidity.

Furthermore, at present there is no satisfactory method forstraightening kinky hair.

Accordingly, it is an object of the present invention to prepare novelcosmetic compositions.

Another object is to improve the application of cosmetic compositions tothe body.

An additional object is to overcome the tendency of mascara to run whenwet.

3,574,822 Patented Apr. 13, l971 A further object is to protect the bodyagainst the drying effects of cosmetics comprising alcohol solutions.

Yet another object is to overcome the greasiness present in variouscosmetic creams, sticks, and lotions.

A still further object is to reduce the staining or soiling property ofcosmetic creams and lotions.

An additional object is to reduce the loss of flavors or essences fromcosmetic compositions.

A corollary object is to develop cosmetic compositions which release aflavor or essence when wet.

An important object of the invention is to straighten kinky or curylhair so that it can be manipulated as desired.

A related object is to set hair of any type.

A further object is to develop a hair setting composition and methodwhich will provide a permanent set even under conditions of highhumidity.

A related object is to give hair a permanent that does not result in thetreated hair developing static electrical charges under conditions oflow humidity.

Another object is to apply a film having one or more of the abovecharacteristics in relation to hair, but which can be readily removed.

A still further object is to develop novel aerosol compositions usefulfor application to the body.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferred embodimentof the invention, are given by way of illustration only, since variouschanges and modifications within the spirit and scope of the inventionwill become apparent to those skilled in the art from this detaileddescription.

It has now been found that these objects can be attained by employingcertain hydrophylic acrylate and methacrylate polymers in cosmeticcompositions. For liquid cosmetics the hydrophylic polymer should nothave substantial cross-linking (is. the cross-linking should not besufficient to render the polymer insoluble in the solvent) while forpowdered or creamy compositions crosslinked copolymers can be employed.

The term cosmetic is intended to embrace all types of products which areto be applied in any manner directly to the person for the purpose ofcleansing or embellishment, including altering the appearance. Toiletsoap and shaving soaps and creams are intended to be included in thisdefinition as well as deodorants, depilatories suntan and sunscreenpreparations.

The hydrophylic monomer used to prepare the hydrophyhc polymer ispreferably a hydroxyalkyl monoacrylate or methacrylate such as2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycolmonoacrylate, diethylene glycol monomethacrylate, hydroxypropylacrylates and methacrylates, e.g. Z-hydroxypropyl acrylate,2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropylmethacrylate, tetraethylene glycol monomethacrylate, pentaethyleneglycol monomethacrylate, dipropylene glycol monomethacrylate,dipropylene glycol monoacrylate. Acrylamide, methacrylamide, diacetoneacrylamide, methylolacrylamide and methylol methacrylamide also areuseful hydrophylic monomers. The most preferred monomer isZ-hydroxyethyl methacrylate and the next most preferred monomer isZ-hydroxyethyl acrylate.

In preparing hydroxyalkyl acrylates and methacrylates a small amount ofthe diacrylate or dimethacrylate is also formed. This need not beremoved as it does not cause undue cross-linking.

When it is desired to shampoo out the hydrophylic polymer there aredesirably included 0.1 to 15% of an ethylenically unsaturated acid toprovide free acid groups. Typical examples of such acids include acrylicacid, methacrylic acid, itaconic acid, aconitic acid, cinnamic acid,crotonic acid, citraconic acid, measaconic acid, maleic acid and fumaricacid. Less preferably there can also be used partial esters of polybasicacids such as mono 2-hydroxypropyl itaconate, mono 2-hydroxyethylitaconate, mono 2-hydroxyethyl citraconate, mono-2-hydroxypropylaconitate, mono 2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate,monomethyl itaconate, monoethyl itaconate, mono methyl Cellosolve esterof itaconic acid (methyl Cellosolve is the monomethyl ether ofdiethylene glycol), mono methyl Cellosolve ester of maleic acid.

The use of such acid containing groups does not result in substantialcross-linking unless the polymer is heated for a substantial time abovenormal operating conditions for cosmetics or unless the polymerizationtime is prolonged using relativel high amounts of catalysts.

When cross-linked or cross-linkable hydrophylic polymers are preparednormally the cross-linking agent is preferably present in an amount of0.1 to 2.5%, most preferably 0.1 to 1.0%, of the total monomers,although up to 15% of cross-linking agent can be used. Typical examplesof cross-linking agents include ethylene glycol diacrylate, ethyleneglycol dimethacrylate, 1,2-butylene dimethacrylate, 1,3-butylenedimethacrylate, 1,4-butylene dimethacrylate, propylene glycoldiacrylate, propylene glycol dimethacrylate, diethylene glycoldimethacrylate, dipropylene glycol diacrylate, divinyl benzene, divinyltoluene, diallyl tartrate, allyl pyruvate, allyl malate, divinyltartrate, triallyl melamine, N,N'-methylene-bisacrylamide, glycerinetrimethacrylate, diallyl maleate, divinyl ether, diallyl mono ethyleneglycol citrate, ethylene glycol vinyl allyl citrate, allyl vinylmaleate, diallyl itaconate, ethylene glycol diester of itaconic acid,divinyl sulfone, hexahydro-1,3,5-triacryltriazine, triallyl phosphite,diallyl ester of benzene phosphonic acid, polyester of maleic anhydridewith triethylene glycol, polyallyl sucrose, polyallyl glucose, e.g.diallyl sucrose and triallyl glucose, sucrose diacrylate, glucosedimethacrylate, pentaerythritol diacrylate, sorbitol dimethacrylate.

The cross-linked polymers are characterized by being insoluble in thesolvents. Typical examples of suitable cross-linked hydrophilic polymersare those in Wichterle Pat. 2,976,576, Wichterle Pat. 3,220,960, e.g.Examples III, V, VI, VII, and IX, Wichterle Pat. 3,361,858, Examples l,2, 3, 6, 8, 9, 10, and 11, as well as copolymers of 30 parts ethyleneglycol with 0.1 part ethylene glycol bismethacrylate; 54.7 partsethylene glycol monomethacrylate, 17.2 parts diethylene glycolmonomethacrylate and 0.6 part of diethylene glycol dimethacrylate; 80parts ethylene glycol monomethacrylate, 15 parts methacrylamide and 0.4part of ethylene glycol bis-methacrylate; 97 parts ethylene glycolmonomethacrylate, 0.25 part diethylene glycol dimethacrylate and 0.25part ethylene glycol bismethacrylate; 60 parts ethylene glycolmonomethacrylate, 19.7 parts diethylene glycol monomethacrylate, 0.3part ethylene glycol bis-methacrylate, 99.6 parts ethylene glycolmonomethacrylate and 0.4 part ethylene glycol bismethacrylate, 99.5parts ethylene glycol monomethacrylate and 0.4 part ethylene glycolbis-methacrylate, 99.7 parts ethylene glycol monomethacrylate andethylene glycol bis-methacrylate; 98.7 parts ethylene glycolmonomethacrylate and 0.3 part diethylene glycol dimethacrylate. They canalso be prepared using the procedures set forth in our parentapplication 654,044 or the procedures employed in the specific examplesbelow.

Unless otherwise indicated all parts and percentages are by weight.

The hydrophylic polymers of this invention possess unique propertieswhich are capable of improving a wide range of cosmetic products. Inparticular, they impart to such products a wide range of unusual anddesirable prop erties and effects on the skin and hair, such aslubricity, emolliency, softening and smoothing, resistance to andprotection against the drying effects of alcohol solutions, resistanceto water and/ or soap or detergents and water, freedom from tactilegreasiness or oiliness due to mineral and/or vegetable oils, markedsolvency and coupling effects for lanolin, lanolin isolates andderivatives either alone or in the presence of mineral and vegetableoils and freedom from tackiness or greasiness in preparations containingany of the above-mentioned materials.

Considering specific applications of the hydrophilic polymers; they areuseful in creams, which essentially comprise an oleaginous base, eitheras an addition thereto or to replace, at least in part, oily fatty and/or waxy ingredients of the creams. For example, the polymers may partlyreplace the almond oil, mineral oil, lanolin, beeswax, paraffin wax,oleic acid, or spermaceti, and the like, which are conventionally usedin creams, whether of the cleansing, emollient, or finishing types, andincluding cold cream, quick-liquefying cream, liquid cleanser cream,night crea'm, massage cream, vanishing cream, foundation cream, andvarious special creams. An advantage of replacing at least part of suchmaterials is that the soiling tendency of the creams is reduced, that isto say, the creams after being spread over the skin by the user are lessapt to pick up or attract soil or foreign particles, similarly, thedeposited creams transfer olf the users skin less readily, as by contactwith clothing, bed sheets, and the like. This last advantage is ofparticular importance in other creams such as deodorants, includingdeodorizer and anti-perspirant creams, which are used under the arms andon the palms and soles and which are quite apt to come in contact withclothing and to soil it to such an extent that the garments arefrequently ruined. The lanolin, petrolatum, cresin, beeswax, cocoabutter, and/or stearic acid contents of emollient and vanishing creams,and also of cream and paste rouges, can be partly supplanted to reducetheir soiling tendency, and more particularly to reduce their oily orgreasy feel While yet retaining their power of free motion over theskin. Because they are lubricitous in a cream preparation withoutincreasing its oleaginous character, cross-linked polymers are suitablefor addition to creams to be applied to the oily skin.

Special creams such as protective creams can usefully incorporate thepolymers of this invention. The creams can be of any suitable type, suchas a mixture of fats and oils, a jelly containing a physical barrier, anemulsion, or a soap base. These creams are of particular value forprotecting the hands from injury, or from soiling, in carrying out manyprocesses and procedures in industrial plants. These creams containingphysical barriers are particularly adapted to receive the hydrophylicpolymers, which being available in various particle sizes, may formprotective barriers on the skin of varying degrees of fineness andsmoothness.

Make-up powders for the face may benefit from the presence of thepolymers. These powders usually comprise an opacifyingagent (clay,titania, magnesia zinc oxide, etc.), a slip material-(talc, metalstearates, etc.), an adherent material (stearates, clay, etc.) and anabsorbent (chalk, calcium carbonate, kaolin, etc.). The hydrophilicpolymers are capable of replacing in whole or in part, metal salts andoxides like chalk, kaolin, magnesium carbonate, talc, titania, magnesiumstearate, zinc oxide, zinc stearate and the like. An advantage of such asubstitution is the reduced incidence of undesirable dermatologicalreactions. For example, in the case of magnesium carbonate, a widelyused ingredient, it is known that some persons are sensitive to thepresence of trace amounts of elements like selenium, arsenic, or mercurywhich tend to be present in the magnesium carbonate owing to thedifficulty of purifying it. The gravity of the problem is underlined bythe fact that amounts of selenium as low as one part per million may bedetrimental. Other conventional ingredients, if not sufiiciently fine,may give rise to mechanical irritation. In the case of ingredients liketalc, by omitting it there is eliminated its characteristic earthy odor,which otherwise must be masked. Of further interest is the effectivenessof the polymers for sorbing oil, this properly being useful in facepowders for combating oily skin, especially on the nose. By sorption ismeant the capacity of the polymeric powder to absorb oily, fatty,greasy, waxy and aqueous materials.

In addition to the foregoing capabilities, the polymers are of benefitto loose face powder compositions by virtue of their excellent adherenceto surfaces including the skin, by the degree to which their particlesize may be varied, and by the extent to which their fiuffiness or bulkdensity may be changed. Therefore, they are useful in place f theadherent agents noted. By incorporating conventional amounts of adesired color and a desired perfume, a complete, esthetically suitableface powder may be made which will inherently have a mat effect, andwhich may be used per se or serve as a base, with or without the colorand perfume, to which only minor additions need be made to obtaindesired finished powders to suit different types of skin.

In compact powders, including face powder and rouge, which are pressedafter the addition of a binder like gum arabic, gum tragacanth,glycerin, sorbitol, etc., the use of the hydrophilic polymers caneliminate the need for the binder as they are inherently compressible inthe dry or wet state to any desired degree.

The polymers are also useful in lipstick compositions and can replaceone or more oleaginous ingredients in whole or part, such as the fatsand waxes, with the advantage or decreased greasiness without loss oflubricity, and improved consistency retention. Fats and waxes which arecommonly used in lipstick compositions include beeswax, carnauba wax,ceresin, lanolin, lard, mineral oil, petrolatum, etc. Conventionallyused lipstick flavors, usually comprising a volatile, water-immiscibleorganic ester, may be better retained in the lipstick owing to the goodsorptive capacity of the polymers for such compounds. The polymers formfree-flowing, apparently dry mixes with flavors, and thus can facilitatelipstick manufacture by serving as a carrier for introducing thesevolatile compounds to the production batch and losses of the flavors maybe reduced.

In mascara preparations such as mascara cake, the polymers can supplantconventional soaps like triethanol amine stearate, triethanolamine,oleate, etc., and thereby render the preparation less irritating to theeyes. The waxes frequently used in these preparations, and also inroll-on mascara and cream mascara, can be at least partly replaced withadvantages similar to those described in wax substitutions. Thehydrophylic polymers of this invention are also capable of imparting acleaner effect to eyelashes, avoiding the thick, pasty, or crumbly lookresulting from the use of some conventional preparations or thestartling effect imparted by some enamel-like preparations. Use of thepolymers permits a wider selecti n of colors to be employed and thus mayavoid dependence on the conventional but somewhat dangerous use ofsilver nitrate with sodium thiosulfate. Suitable colors include naturalpigments, e.g. carbon, ochers, siennas, umbers, ultramarine, etc. Insimilar ways, the polymers are of value to other cosmetics for usearound the eye, as in eye shadow sticks, eye liner pencils, and eyebrowpencils.

The hydrophylic polymers of the invention can improve shaving creams,soaps and sticks of the lathering type by strengthening and stabilizingthe lather.

In sunscreen products, including suntan products and leg paints, thehydrophylic polymers provide lubricity without greasiness, and inaddition, the adherence of the product to the skin is enhanced, and itswater-removability improved. As these preparations are frequently indispersion form, a further advantage resides in the stability which isimparted to the dispersions by the presence of the polymers. Of interestin this connection are simple 2-, 3-, or 4-component sunscreenpreparations made by mixing a base like petrolatum or zinc oxide orlanolin with the hydrophilic polymer and water. A sunburn preventive canbe added to help block out harmful radiation, including such agents asacetanilide, chloesterol, paminobenzoic and salicylic acid salts,quinine salts, and the like. These components form compatible mixtures.Suntan make-up, whether in loose powder form for the face and otherareas, or in cake form, can be benefited in the manner described formake-up powders.

In manicure compositions, water removable nail coat- 1ng compositionscan be prepared comprising simply a hydrophilic polymer of thisinvention, a coloring agent, and solvent. The polymers provides thenecessary adherence to the nails. Such compositions are of value forapplication to the nails for a single occasion of short duration, afterwhich the coatings are removable by simply washing the hands in water.

The polymers of this invention are also effective in hair preparations.

The present invention overcomes the disadvantages pointed out supra ofprevious hair preparations. Even though the hydrophylic polymers of theinvention are insoluble in water, they are easily removed, e.g. withconventional shampoo.

Hair sprays produced according to this invention comprise a solublehydrophylic polymer such as previously described and a non-toxic organicsolvent. When an aerosol is to be prepared then a propellant is alsoused. As the organic solvent there can be employed alcohols,particularly lower aliphatic saturated alcohols e.g. ethyl alcohol,isopropyl alcohol, propyl alcohol, glycols, e.g. ethylene glycoldiethylene glycol, propylene glycol and dipropylene glycol, glycerine,ethylene glycol methyl ether, ethylene glycol ethyl ether, n-propyleneglycol monomethyl ether, n-propylene glycol monoethyl ether,isopropylene glycol monomethyl ether, isopropylene glycol monoethylether, ethyl acetate. Mixtures of these solvents with minor amounts ofwater, e.g. up to 30% water, can be also employed. Glycols and glycerineand similar polyhydric alcohols act as plasticizers for the hydrophylicpolymer.

Generally the amount of hydrophylic polymer will be about 0.5 to 10%,preferably 0.75 to 5%, by weight of the total hair spray composition.

Hair setting and hair straightening compositions are also producedaccording to the invention using 0.5 to 10% of the hydrophylic polymerin the solvent.

Such compositions not only provide the desired ternporary set-holdingcharacteristics and maintains the hair in the desired configurationuntil removed, but do so even when the hair is exposed to conditions ofhigh humidity without the development of any appreciable surface track.In addition, the hair thus treated, despite its resistance to moisture,is remarkably free from any tendency to develop static electricalcharges when combed or brushed under conditions of low humidity.Furthermore, the treated hair is capable of being reset merely by use ofwater-dampened comb. Finally, the film on the hair may readily beremoved, despite its resistance to moisture, by a mild shampoo.

The hydrophylic polymers can be used not only in solution, but also incompositions having the form of stable gels, creams and the like withoutrequiring the presence of an emulsifying agent. They can have thephysical form of a jelly, paste, plastic mass, or the like and generallycomprise the hydrophylic polymer in an amount of 2 to 15% by weight ofthe total composition. Advantageously there can be included 7 to 20% ofa thixotropic agent such as Carbopol 961 (sucrose acrylate having freeacid groups).

The amount of solvent is usually 10% or more of the total hairpreparation. When a propellant is present the solvent is normally notover 60% and is preferably 25 to 40% of the total hair preparation byweight.

When the hydrophylic polymer is packaged in an aerosol container thepropellant should be sufficient to forc the composition out of thecontainer as a spray. The propellant can vary considerably, but usuallyis about 25 to 85%, preferably 50 to 70%, of the total hair spraycomposition. As the aerosol propellants there can be used compressedgasses such as carbon dioxide, nitrous oxide and nitrogen, liquifiedvolatile hydrocarbons such as propane, n-butane, isobutane, Z-methylbutane and fluorinated compounds including perhalogenated compounds andfiuorinated hydrocarbons such as dichlorodifiuoromethane,trichlorofiuoromethane, 1,2-dichlorotetrafluoroethane,octofluorocyclobutane, chlorodifiuoromethane, 1,1- difluoroethane,l-chloro-1,1-difluoroethane. These fluorinated compounds are availableunder the names Freon and Genetron. The propellant should contain asubstantial amount of volatile material boiling at not over 20 C., butthere can also be present a significant amount of less volatile materialboiling up to 50 C., e.g. methylene chloride can be present as asubstantial part of the propellant. Of course perfumes or other essencescan be included in the formulations.

As catalysts for carrying out the polymerization there is employed freeradical catalyst in the range of 0.05 to 1% of the polymerizablehydroxyalkyl ester, for example, the preferred amount of catalyst is 0.1to 0.2% of the monomer. Typical catalysts include t-butyl peroctoate,benzoyl peroxide, isopropyl percarbonate, methylethylketone peroxide,cumene hydroperoxide and dicumylperoxide. Irradiation, e.g., by ultraviolet light or gamma rays, also can be employed to catalyze thepolymerization. Polymerization can be done at 20 to 150 C., usually 40to 90 C.

When cross-linked polymers are prepared the method of polymerization isnot critical and the monomers can be polymerized in water, by suspensionpolymerization, in organic solvent or without any solvent. Howev r, whenhydrophylic soluble thermoplastic polymers are desired they arepreferably prepared by suspension polymerization of the hydrophylicmonomers in a non-polar medium such as silicone oil, mineral oil,xylene, toluene, benzene or the like. Alternatively they can bepolymerized while in solution in ethyl alcohol, methyl alcohol, propylalcohol, isopropyl alcohol, formamide, dimethyl sulfoxide or otherappropriate solvent.

In the suspension polymerization procedure the catalyst containingmonomer is dispersed in the non-polar medium in the form of smalldroplets which are polymerized to form finely divided spheres or beads.The beads are dissolved in the polar organic solvents, e.g., ethylalcohol, isopropyl alcohol, ethyl alcohol-water (e.g. 95:5 or 70:30),glycols and glycol ethers for use as sprays, etc. or are mixed withother ingredients to make creams, powders or the like.

Suspension polymerization is preferably carried out at 50150 C. untilbead formation is completed. The ratio of suspension oil to monomer canbe varied Widely, but preferably is from 5:1 to 20:1. As stated thecatalyst to monomer ratio is preferably from 0.05 to 1.0 part per 100parts of monomer.

One method of incorporating the hydrophylic polymeric powders withcosmetic ingredients or essences dissolved in an appropriate solvent isto place the mixture on a mechanical roller so that the solution becomesintimately mixed with the powder. The mixture is dried by airevaporation or forced heat. Upon evaporation of the solvent the cosmeticingredients and/or essences are retained by the powder.

EXAMPLE 1 Into a flask equipped with an agitator and a heating mantlewas charged 1000 grams of silicone oil; polydimethyl silicone, 100 gramsof 2-hydroxyethyl methacrylate and 0.33 gram of isopropyl percarbonate.The flask Was placed under a nitrogen atmosphere and the contents wererapidly agitated and heated to 100 C. After 15 minutes at 100 C., thepolymer slurry obtained was filtered hot to isolate the polymer. Thepolymer powder was reslurried in 300 ml. of xylene, filtered and dried.A 98% yield of 2 to 5 micron particle size powder was obtained.

EXAMPLE 2 The thermoplastic, solvent soluble polY-(Z-hydroxyethylmethacrylate) polymeric powder formed in Example 1 was mixed with an oilof orchids perfume essence and the resultant mixture placed on amechanical roller for approximately 8 hours. The polymeric powder thusabsorbed the essence. The mixture was filtered and the residue dried atroom temperature.

EXAMPLE 3 Example 1 was repeated using xylene in place of the siliconeoil. The amount of Z-hydroxyethyl methacrylate was increased from 100grams to 300 grams and the quantity of isopropyl percarbonate wasincreased to 0.99 gram. An yield of polymer beads was obtained.

EXAMPLE 4 Example 1 was repeated using mineral oil in place of thesilicone oil, the amount of 2-hydroxyethyl methacrylate was increasedfrom grams to 200 grams and the quantity of isopropyl percarbonate wasincreased from 0.33 to 066 gram. A 98% yield of polymer beads ranging indiameter from 2 to 5 microns was obtained.

EXAMPLE 5 800 grams of ethylene glycol monomethyl ether, grams of2-hydroxyethyl methacrylate, 20 grams of acrylic acid and 2 grams oft-butyl peroctoate were charged into a flask. The solution was heatedand stirred under a carbon dioxide atmosphere at 85 C. for 6 hours. Thethermoplastic hydrophylic polymer formed was precipitated by pouring thereaction solution into 10 liters of rapidly agitated water. Theprecipitated polymer Was isolated by filtration and dried. The productof this example while thermoplastic and solvent soluble has thecapability of curing to cross-linked solvent insoluble polymer byfurther heating, particularly if additional catalyst is added. Incontrast, the polymers of Examples 1, 3, and 4 are permanentlythermoplastic and solvent soluble. The copolymers formed in Examples7-13 are all cross-linked.

EXAMPLE 6 The procedure of Example 1 was repeated replacing theZ-hydroxyethyl methacrylate by 100 grams of 2-hydroxypropyl methacrylateto produce a thermoplastic solvent soluble hydrophylic finely dividedbead polymer.

EXAMPLE 7 This example shows the preparation of a cross-linked polymerprepared with the aid of a foaming agent. The use of a foaming agent,e.g. sodium bicarboante, potassium bicarbonate, azodicarbonamide,benzene sulfonyl hydrazide, azo-bis-isobutyronitrile, etc. aids inpreparing polymers which are in the form of a foam which is easilydisintegrated to form a fine powder by means of a shearing action.Quantities of 0.5 to 10 grams of foaming agent per 100 grams ofreactants are adequate.

100 grams of Z-hydroxyethyl methacrylate, 0.15 gram of t-butylperoctoate, 0.20 gram of ethylene glycol dimethacrylate and 1 gram ofsodium bicarbonate were heated to 70 C. and the resulting solid friablepolymeric foam ground into a powder of 80 mesh size (US. standardsieve).

EXAMPLE 8 100 grams of purified Z-hydroxyethyl methacrylate was mixedwith 0.2 gram of ethylene glycol dimethacrylate and 1 gram of benzoylperoxide. The mixture 'was sprayed via a nozzle which forms finedroplets into a chamber containing nitrogen at 150C. After spraying ofthe monomer was concluded, 36 grams of polymer beads were recovered.

EXAMPLE 9 An aqueous solution was prepared from 15% acrylamide, 10%ethylene glycol monomethacrylate, 0.1% ethylene glycol dimethacrylateand the balance water. One liter of this solution was mixed with 10 ml.of an aqueous 2% solution of sodium thiosulfate and 15 ml. of an aqueous2% solution of ammonium persulfate and the mixture allowed to polymerizeat room temperature. The resulting gel was then finely divided to give acrosslinked hydrophylic polymer.

EXAMPLE 10 A polymerization mixture was prepared from 15 partsrnethacrylamide, 80 parts ethylene glycol monomethacrylate, 0.4 partethylene glycol bis-methacrylate and 5 parts of dibenzoyl peroxide. Themixture was rotated at 400 r.p.m. in a helium atmosphere at 80 C. for 6hours to give a cross-linked copolymer. The polymer was then finelydivided (below 100 mesh).

EXAMPLE 11 97 parts of ethylene glycol monomethaerylate, 0.25 partethylene glycol bis-methacrylate, 0.25 part diethylene glycolbis-methacrylate, 2 parts ethylene glycol and 0.2 part diisopropylpercarbonate were rotated 80 minutes at 420 r.p.m. in a carbon dioxideatmosphere at 60 C. to produce a cross-linked hydrophylic copolymer. Thepolymer Was then finely divided, i.e. to less than 100 mesh.

EXAMPLE 12 15 parts of a monomer mixture consisting of 99.7% ethyleneglycol monomethacrylate and 0.3% ethylene glycol bis-methacrylate as across-linking agent, 85 parts glycerol and 0.1 part diethyl percarbonateas a catalyst was heated at 65 C. for 20 minutes to form a crosslinkedhydrophylic polymer.

EXAMPLE 13 50 m1. of a mixture of 98% ethylene glycol mono methacrylate,0.3% diethylene glycol bis-methacrylate and 1% ethylene glycol weremixed with 5 0 ml. formamide and an amount of azo-bis-isobutyronitrilecorresponding to 0.2% of the combined monomers. Polymerization wasperformed at 75 C. for 50 minutes to give a cross-linked hydrophylicpolymer.

EXAMPLE 14 30 grams of the solvent soluble, thermoplastic hydro phylicpoly(2-hydroxyethyl methacrylate) prepared in Example 1 was dissolved in70 ml. of methanol. To the solution was added 4.0 grams of peppermintoil. The viscous solution was coated on an impervious plate and allowedto dry to form a film 1.0 mil thick. The dry film was stripped from theplate and ground to form minute platelets. These were incorporated in anamount of about 1% in crest-type toothpaste devoid of flavoring toprovide prolonged release of the peppermint flavor on contact of theproduct with an aqueous medium, e.g. in the normal brushing of teeth.

The toothpaste formula was:

Parts Hydrophylic polymer platelets containing pepper- 5 mint oil 1Calcium pyrophosphate 39 Sodium carboxymethyl cellulose 1.20 Magnesiumaluminum silicate 0.40

Sorbitol 20.00 Sodium coconut monoglyceride sulfonate 0.81 Sodium laurylsulfate 0.70 Saccharin 0.12 Stannous pyrophosphate 1.00

Water 25.77

10 EXAMPLE 15 A hair setting composition was prepared from 1.90 parts ofthe poly 2-hydroxyethyl methacrylate prepared in Example '1, 0.10 partof perfume (oil of orchids) and 28 parts of ethyl alcohol. This solution(50% of the total formulation) was packaged in a conventional aerosolpressure can container together with 45.5 parts (32% of the totalformulation) of monofluorotrichloromethane and 24.5 parts (18% of thetotal) of methylene chloride.

The aerosol was sprayed on hair held in a desired configuration andallowed to dry, the formulation was found to provide satisfactoryset-holding characteristics even under conditions of high humidity. Thesprayed hair was natural looking, non-sticky, non-static and exhibitedholding power for a relatively long period of time.

EXAMPLE 16 A 5% solution of the polymeric 2-hydroxyethyl methacrylateprepared in Example 1 in ethyl alcohol (95% alcohol, 5% water) wasapplied to kinky hair. The hair was relaxed and then rolled on rollersand held in tension until dried. When dry the hair was set and could becombed in conventional fashion. The permanent remained until the hairwas Wet.

Drying can be accomplished with or without a conventional hair dryer. Inplace of the rollers any other conventional means for holding the hairin tension can be employed.

EXAMPLE 17 A more flexible wave can be obtained by incorporating 5 tobased on the polymer, of glycerol, sorbitol, diethylene glycol,dipropylene glycol, ethylene glycol, propylene glycol or other liquidpolyhydric alcohol as a plasticizer.

Thus a more flexible wave than that of Example 16 was obtained byapplying to the hair, a solution of 5 parts of the poly 2hydroxyethylmethacrylate, 100 parts of 95 ethyl alcohol and 0.75 part of glycerol.After the hair was relaxed it was held in tension until dried using ahair dryer. The hair was thus set and was combed in conventional manner.Not only was a more flexible wave obtained, but the use of glycerolprevented flaking of the polymer when the hair was combed.

EXAMPLE 18 To impart greater sheen to the hair a small amount, e.g. 23%,of silicone oil can be added to the formulation. Thus the formulation ofExample 17 was modified by adding 3% of dimethyl polysiloxane oil basedon the 2-hydroxyethyl methacrylate polymer to give a flexible permanentwave having a high sheen.

The hair straightener compositions can be brushed on the hair, poured onthe hair or combed on the hair. The preferred solvent is ethyl alcoholwith or without minor amounts of water. There can also be employed othersolvents such as isopropyl alcohol, monomethyl ether of ethylene glycol,monoethyl ether of ethylene glycol, normal or isopropylene glycolmonomethyl ether, normal or isopropylene glycol monoethyl ether.

EXAMPLE 19 A hair setting gel was produced having the followingformulation:

Parts Hydrophylic Z-hydroxyethyl methacrylate polymer of Example 1 1095% ethyl alcohol 144 Water 36 Carbopol 940 (sucrose acrylate polymerhaving free acrylic acid groups) 1.2 Glycerine 1.4 Solulan 9-8(acetylated polyoxyethylated lanolin) 1.0

Triton X-100 (polyoxyethylene (10)-nonylphenol condensate) 2.0 Essence(lavender oil) 0.6

The polymer was dissolved in the alcohol-water mixture to form asolution. The solution was then mixed with the remaining ingredients byrapid stirring and the pH of the mixture adjusted to a pH of about 7.2by adding a 10% solution of diisopropanolamine in 95% ethyl alcohol.This gel was suitable for setting hair. Thus a sample of curly hair wasstraightened by heat and pressure, coated with the above gel and soakedin water. A control sample of the curly hair was also straightened, butremained uncoated when soaked in water. The control sample returned toits original curly configuration after 30 seconds while the coatedsample remained straight for about 3 minutes.

In place of the diisopropanolamine there can also be usedtriethanolamine, diethanolarnine or tripropanolamine as a gelling agentin this example.

EXAMPLE 2O Into a bottle equipped with an agitator and a heating mantlewas charged 20 liters of 2-hydroxy ethyl methacrylate, 50 liters ofmethanol, 30 liters of water and 10 grams of t-butyl peroctoate. Thekettle was flushed with carbon dioxide and the contents were rapidlyagitated and heated to 75 C. After 8 hours at 75 C. the polymer,representing an 85% polymeric conversion, was isolated. The polymersolution was precipitated from 500 liters of water, filtered and driedat room .temperature.

Solution A is added slowly to solution B with rapid stirring forminutes. A stable emulsion results which could be applied to the handsor face. Polysorbate 80 is polyoxyethylene (20) sorbitan monooleate.

EXAMPLE 22 An insect repellant sun screen lotion was prepared with thefollowing formulation:

Parts Hydrophylic polymer of Example 1 1 95% ethanol 60 Water 382-ethyl-1,3-hexandiol 0.5 2-ethoxyethyl-p-methoxy cinnamate 0.5

EXAMPLE 23 100 parts of the hydrophylic polymer prepared in Example 1containing parts of essence (oil of orchids) was homogeneously mixedwith 5 parts of hexachlorophene. 75 parts of the resulting mixture, wasmixed with a conventional toilet soap (Ivory) to provide a compositesoap having a pleasant smell, antiseptic and increased lubricitycharacteristics.

EXAMPLE 24 The hydrophylic polymers of the present invention in powderform can be incorporated in a fat or oil or lanolin in an amount of l to40% to release a fragrance on contact with water. Thus 1 part of perfumewas absorbed in 10 parts of the cross-linked hydrophylic polymer prepared in Example 7 and this was incorporated with 100 parts of lanolin.

1 2 EXAMPLE 25 A sun screen aerosol was made from 1 part of the poly2-hydroxyethyl methacrylate prepared in Example 1, 30 parts of ethylalcohol, 0.5 part of 2-ethoxyethylp-methoxy cinnamate and 68.5 parts ofdichlorotetrafluo roethane. The aerosol was sprayed from the containeronto the body and acted as an elfective sun screen.

EXAMPLE 26 20 parts of aluminum chlorohydrol, in parts of water, 10parts of hydroxyethyl methacrylate containing 1 part of perfume (e.g.rose oil) and 0.04 part of isopropyl percarbonate were polymerized at 70C. for two hours. The solid obtained was ground to a powder--less than300 mesh and was useful as a deodorant by applying the same to the body.

EXAMPLE 28 A nail enamel was prepared by making a 10% solution of thepolymer prepared in Example 1 in alcohol together with a small amount ofred dye. The resulting solution was applied to fingernails and allowedto dry.

EXAMPLE 29 A cleansing cream was prepared from a mixture of 5 partsalmond oil, 15 parts lanolin, 5 parts of the hydrophylic 2-hydroxyethylmethacrylate polymer prepared in Example 1, 30 parts parafiin wax, 5parts borax and 35 parts distilled water.

EXAMPLE 30 Another cleansing cream was prepared from 25 parts almondoil, 10 parts beeswax, 15 parts lanolin, 8 parts spermaceti, 12 parts ofthe hydrophylic cross-linked polymer of Example 11 and 30 parts of rosewater.

EXAMPLE 31 A cleansing cream was prepared from 7 parts beeswax, 30 partsmineral oil, 15 parts soybean oil, 10 parts spermaceti, 1 part borax, 8parts of the hydrophylic polymer prepared in Example 6 and 29 parts ofrose water.

EXAMPLE 32 A vanishing foundation cream was prepared from 8 partsglycerol, 1 part potassium hydroxide, 20 parts stearic acid, 0.5 partperfume, 7 parts of the hydrophylic polymer of Example 1 and 63.5 partsof water.

EXAMPLE 33 A vanishing cream was prepared from 0.5 part cetyl alcohol, 5parts glycerol, 4 parts lanolin, 3 parts mineral oil, 20 parts stearicacid, 2 parts triethanolamine, 0.5 part oil of orchids, 3 parts of thehydrophylic polymer prepared in Example 5 and 62 parts of water.

EXAMPLE 34 A quick-liquefying hand cream was made from 12 parts cresin,85 parts mineral oil and 3 parts of the hydrophylic polymer prepared inExample 4.

EXAMPLE 35 An emollient cream for softening the skin was prepared from 5parts lanolin, 4 parts beeswax, 10 parts cocoa butter, 10 parts almondoil, 35 parts solid petrolatum, 5 parts spermaceti, 3 par-ts of thehydrophylic polymer prepared in Example 1, 0.5 part of perfume, 0.2 partpreservative and 27.3 parts water.

EXAMPLE 3 6 A face powder was made from 10 parts precipitated chalk, 75parts talc, parts of the hydrophylic polymer of Example 1, 5 parts zincoxide and 5 parts zinc stearate.

EXAMPLE 37 A loose face powder was prepared from 3 parts kaolin, 70parts talc, 1.5 parts magnesium stearate, 2 parts of D & C Red No. 2(lake) 20% in talc, D & C Red No. 3 (lake) tale, 1 part yellow ironoxide in talc and 1 part rose oil absorbed in 4.5 parts of thehydrophylic polymer of Example 7.

EXAMPLE 38 EXAMPLE 39 A baby powder was prepared from 80 parts talc, 9parts zinc stearate, 5 parts boric acid and 0.25 part perfume absorbedin 5.75 parts of the hydrophylic polymer prepared in Example 1.

EXAMPLE 40 A lipstick was prepared from 12 parts beeswax, 3 parts of thehydrophylic polymer of Example 1, 5 parts carnauba wax, 20 partsceresin, 5 parts lanolin, 28 parts lard, 15 parts mineral oil, 2 partsof dibromo fluorescein and 10 parts of lakes (a mixture of equal partsof D & C No. 9 and D & C Orange No. 4).

What is claimed is:

1. In a process of improving the external appearance of the human bodyby applying to the body a cosmetic preparation the improvementcomprising applying a cosmetic composition in powder form including apolymer powder of an acrylate or methacrylate selected from the groupconsisting of hydrophilic polymer of hydroxy lower alkyl acrylates,hydroxy lower alkyl methacrylates, hydroxy lower alkoxy lower alkylacrylates and hydroxy lower alkoxy lower alkyl methacrylates.

2. A process according to claim 1 wherein the cosmetic compositionincludes a deodorant and the deodorant is applied to the skin.

3. A process according to claim 2 wherein the composition is applied asa dry powder.

4. A porcess according to claim 3 wherein the composition is applied inthe form of an aerosol spray.

5. A process according to claim 4 wherein the polymer is a2-hydroxymethyl methacrylate powder.

6. A process according to claim 1 wherein the cosmetic composition is adry powder and the powder is applied to the skin in the form of anaerosol spray and the acrylate powder or methacrylate is a member of thegroup consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate,hydroxypropyl acrylate and hydroxypropyl methacrylate.

7. A process according to claim 1 wherein said polymeric powder iscross-linked and solvent insoluble.

8. A process according to claim 7 wherein the acrylate or methacrylatepowder comprises a cross-linked and solvent insoluble polymer of amember of the group consisting of hydroxyethyl acrylate, hydroxyethylmethacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

9. A process according to claim 1 wherein said polymeric powder issolvent soluble.

10. A process according to claim 9 wherein the solvent soluble acrylateor methacrylate comprises a polymer of a member of the group consistingof hydroxyethyl acrylate, hydroxymethyl methacrylate and hydroxypropylmethacrylate.

11. A process according to claim 9 wherein the polymer is a polymer of2-hydroxyethyl methacrylate.

12. A process according to claim 1 wherein the cosmetic preparation is acosmetic powder and the powder is applied to the skin.

References Cited UNITED STATES PATENTS 2,976,576 3/1961 Wichterle et al.18-58 3,220,960 11/1965 Wichterle et al. 260-25 3,269,903 8/1966 VonFieandt et al. 424-81 3,428,043 2/1969 Shepherd 128-268 3,400,890 9/1968Gould 239-36 SHEP K. ROSE, Primary Examiner US. Cl. X.R.

